US6475647B1 - Protective coating system for high temperature stainless steel - Google Patents
Protective coating system for high temperature stainless steel Download PDFInfo
- Publication number
- US6475647B1 US6475647B1 US09/690,447 US69044700A US6475647B1 US 6475647 B1 US6475647 B1 US 6475647B1 US 69044700 A US69044700 A US 69044700A US 6475647 B1 US6475647 B1 US 6475647B1
- Authority
- US
- United States
- Prior art keywords
- coating
- aluminum
- thickness
- stainless steel
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime, expires
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 33
- 239000010935 stainless steel Substances 0.000 title claims abstract description 26
- 239000011253 protective coating Substances 0.000 title 1
- 238000000576 coating method Methods 0.000 claims abstract description 105
- 239000011248 coating agent Substances 0.000 claims abstract description 92
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Chemical group 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 16
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004939 coking Methods 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Chemical group 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 53
- 239000000956 alloy Substances 0.000 claims description 53
- 239000011651 chromium Substances 0.000 claims description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 34
- 229910052804 chromium Inorganic materials 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- 239000002344 surface layer Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000001464 adherent effect Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 239000000571 coke Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 150000004767 nitrides Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005269 aluminizing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000601 superalloy Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000002352 steam pyrolysis Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BKUKXOMYGPYFJJ-UHFFFAOYSA-N 2-ethylsulfanyl-1h-benzimidazole;hydrobromide Chemical compound Br.C1=CC=C2NC(SCC)=NC2=C1 BKUKXOMYGPYFJJ-UHFFFAOYSA-N 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910008332 Si-Ti Inorganic materials 0.000 description 1
- 229910006749 Si—Ti Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/938—Vapor deposition or gas diffusion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/939—Molten or fused coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/941—Solid state alloying, e.g. diffusion, to disappearance of an original layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/919—Apparatus considerations
- Y10S585/92—Apparatus considerations using apparatus of recited composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12583—Component contains compound of adjacent metal
- Y10T428/1259—Oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12937—Co- or Ni-base component next to Fe-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
- Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
Definitions
- the present invention relates to a coating system for the generation of protective surface alloys for high temperature metal alloy products and, more particularly, relates to the provision of a metal alloy coating on the internal wall surfaces of high-temperature stainless steel tubes to produce a coating that provides corrosion resistance and reduces the formation of catalytic coking in hydrocarbon processing such as in olefin production and in direct reduction of ores.
- Stainless steels are a group of alloys based on iron, nickel and chromium as the major constituents, with additives that can include carbon, tungsten, niobium, titanium, molybdenum, manganese, and silicon to achieve specific structures and properties.
- the major types are known as martensitic, ferritic, duplex and austenitic steels.
- Austenitic stainless steel generally is used where both high strength and high corrosion resistance is required.
- One group of such steels is known collectively as high temperature alloys (HTAs) and is used in industrial processes that operate at elevated temperatures generally above 650° C. and extending to the temperature limits of ferrous metallurgy at about 1150° C.
- HTAs high temperature alloys
- the major austenitic alloys used have a composition of iron, nickel or chromium in the range of 18 to 41 wt % chromium, 18 to 48 wt % nickel, balance iron and other alloying additives.
- high chromium stainless steels have about 31 to 38 wt % chromium and low chromium stainless steels have about 20 to 25 wt % chromium.
- the bulk composition of HTAs is engineered towards physical properties such as creep resistance and strength, and chemical properties of the surface such as corrosion resistance. Corrosion takes many forms depending on the operating environment and includes carburization, oxidation and sulfidation. Protection of the bulk alloy is often provided by the surface being enriched in chromium oxide (chromia) and aluminum oxide (alumina).
- chromia chromium oxide
- alumina aluminum oxide
- compositions of stainless steels for high temperature use are tailored to provide a balance between good mechanical properties and good resistance to oxidation and corrosion. Alloy compositions which can provide an alumina scale are favoured when good high temperature oxidation resistance is required, whereas compositions capable of forming a chromia scale are selected for resistance to hot corrosive conditions.
- the addition of high levels of aluminum to the bulk alloy is not compatible with retaining good mechanical properties. Therefore applying a coating containing aluminum onto the bulk alloy is a good way to provide the desired alumina surface oxide while maintaining desired mechanical properties.
- olefins such as ethylene by hydrocarbon steam pyrolysis (cracking).
- Hydrocarbon feedstock such as ethane, propane, butane or naphtha is mixed with steam and passed through a furnace coil made from welded tubes and fittings. The coil is heated on the outerwall and the heat is conducted to the innerwall surface leading to the pyrolysis of the hydrocarbon feed to produce the desired product mix at temperatures in the range of 850 to 1150° C.
- An undesirable side effect of the process is the buildup of coke (carbon) on the innerwall surface of the coil.
- catalytic coke or filamentous coke
- a catalyst such as nickel or iron
- amorphous coke that forms in the gas phase and plated out from the gas stream.
- catalytic coke can account for 80 to 90% of the deposit and provides a large surface area for collecting amorphous coke.
- the coke builds up and constricts flow in the tubes and acts as a thermal insulator, requiring a continuous increase in the tube outer wall temperature to maintain throughput.
- a point is reached when the coke buildup is so severe that either the pressure drop reaches unacceptable levels or the tube skin temperature cannot be raised any further and the furnace coil is then taken offline to remove the coke by burning it off (decoking).
- the decoking operation typically lasts for 24 to 96 hours and is necessary once every 10 to 180 days. During a decoke period, there is no marketable production which represents a major economic loss. Additionally, the decoke process degrades tubes at an accelerated rate, leading to a shortened lifetime.
- aluminized steels, silica coated steels, and steel surfaces enriched in manganese oxides or chromium oxides are beneficial in reducing catalytic coke formation.
- AlonizingTM, or aluminizing involves the diffusion of aluminum into the alloy surface by pack cementation, a chemical vapour deposition technique.
- the coating is functional to form a NiAl type compound and provides an alumina scale which is effective in reducing catalytic coke formation and protecting from oxidation and other forms of corrosion.
- the coating is not stable at temperatures such as those used in ethylene furnaces, and also is brittle, exhibiting a tendency to spall or diffuse into the base alloy matrix.
- pack cementation is limited to the deposition of one or two elements, the co-deposition of multiple elements being extremely difficult.
- Commercially it is generally limited to the deposition of only a few elements, mainly aluminum.
- Another approach to the application of aluminum diffusion coatings to an alloy substrate is disclosed in U.S. Pat. No. 5,403,629 issued to P. Adam et al. This patent details a process for the vapour deposition of a metallic interlayer on the surface of a metal component, for example by sputtering. An aluminum diffusion coating is thereafter deposited on the interlayer.
- Both of these systems relate to improvement of oxidation and/or hot corrosion resistance imparted to superalloys by the deposition of an MCrAlY thereon.
- These references do not relate to improvement of anticoking properties or corrosion resistance of high temperature stainless steel alloys used in the petrochemical industries.
- Such stainless steels have different chemical compositions and have higher levels of elements considered to be impurities. Examples of impurities include embedded nitrogen and carbon which diffuse outward when the alloys are heated and can shorten the life of improperly designed surface coatings.
- a major difficulty in seeking an effective coating is the propensity of many applied coatings to fail to adhere to the tube alloy substrate under the specified high temperature operating conditions in hydrocarbon pyrolysis furnaces. Additionally, the coatings lack the necessary resistance to any or all of thermal stability, thermal shock, hot erosion, carburization, oxidation and sulfidation.
- a commercially viable product for olefins manufacture by hydrocarbon steam pyrolysis and for direct reduction of iron ores must be capable of providing the necessary coking and carburization resistance over an extended operating life while exhibiting thermal stability, hot erosion resistance and thermal shock resistance. It must also be capable of maintaining adherence over time as the impurities of the stainless steels diffuse outward.
- Plasma transferred arc surface is a technique used to apply coatings of different compositions and thickness onto conducting substrates.
- the material is fed in powder or wire form to a torch that generates an arc between a cathode and the work-piece.
- the arc generates plasma that heats up both the powder or wire and surface of the substrate, melting them and creating a liquid puddle, which on solidification creates a welded coating.
- By varying the feed rate of material, the speed of the torch, its distance to the substrate and the current that flows through the arc it is possible to control thickness, microstructure, density and other properties of the coating (P. Harris and B. L.
- the interlayer will then scatter nitrides and carbides that may precipitate inside the coating to avoid forming of an undesirable continuous layer during long term exposure to high temperatures in service.
- a continuous nitride or carbide layer would jeopardize the mechanical integrity of the films by reducing their adhesion to the tube.
- NiCrAlY anti-coking coatings generally need a special heat treatment to cause diffusion between the coating and the HTA tube. This heat treatment also serves the purpose of densifying and stabilizing the coatings. However, the hear treatment is an extra step requiring control of temperature, heating rate and dwell time to successfully produce a high quality coating.
- Another important object of the invention is the provision of a denser, continuous, smooth interface between the alloy coating and the substrate with dispersed precipitated nitrides and carbides to obviate the need for a separate interlayer.
- the coating is deposited in a thickness of about 20 ⁇ m to 6000 ⁇ m, preferably 50 to 2000 ⁇ m
- the MCrAlX preferably is NiCrAlY and has, by weight about 12 to 25% chromium, about 4 to 15% aluminum and about 0.5 to 1.5% yttrium, the balance nickel.
- the deposition of a dense, anti-coking NiCrAlY alloy coating art a single step on a HTA tube by plasma transferred arc deposition produces a gradual metallurgical bond between the alloy coating and substrate.
- the desired final thickness of the coating is between about 0.02 and 6 mm thick.
- the preferred thickness is in the range of 80 to 500 ⁇ m in order to keep powder costs reasonable and to not unduly decrease the inner diameter of the tube.
- an oxygen-containing gas such as air at a temperature above about 1000° C. upon heating of the substrate and coating in a gaseous, oxidizing atmosphere such as air at a temperature above 1000° C. in a separate step, or during commercial use by the introduction of or presence of an oxygen-containing gas at operating temperatures above about 1000° C.
- the more complete the alumina scale the better the anticoking and anti-corrosion performance. Enhanced properties can be therefore sometimes be achieved by a further aluminizing step.
- the high temperature stainless steel substrate having a continuous coating of said MCrAlX alloy with a thickness of about 50 to 2000 ⁇ m, preferably about 80 to 500 ⁇ m may be aluminized by depositing a layer of aluminum on the coating in a thickness up to about 50% of the coating thickness, preferably about 20% of the coating thickness, such as by thermal spray or magnetron sputtering physical vapour deposition.
- FIG. 1 is a photomicrograph of an interface between NiCrAlY overlay coating deposited on a HTA alloy 900B;
- FIG. 2 is a photomicrogaph of a NiCrAlY top surface after 500 hours of aging in air at 1150° C.
- FIG. 3 is a photomicrograph of a bulk microstructure after 500 hours of aging in air at 1150° C.
- FIG. 4 is a photomicrograph of an interface between NiCrAlY overlay coating and a low chromium stainless steel after 500 hours aging in air at 1150° C.
- FIG. 5 is a photomicrograph of an interface between NiCrAlY overlay coating and a high chromium stainless steel after 500 hours aging in air at 1150° C.
- a continuous overlay coating of MCrAlX is deposited onto and metallurgically and adherently bonded to a substrate of a high temperature austenite stainless steel by a plasma transferred arc process.
- the MCrAlX alloy of the invention in which M is a metal selected from the group consisting of iron, nickel and cobalt or mixture thereof and X is an element selected from the group consisting of yttrium, hafnium zirconium and lanthanum or combination thereof comprises, by weight, about 10 to 40% chromium preferably about 10 to 25%, about 3 to 30%, preferably about 4 to 20%, aluminum, and up to about 5%, preferably about 0.5 to 1.5%, yttrium, hafnium zirconium and/or lanthanum, the balance iron, nickel or cobalt.
- the high temperature stainless steel substrate has a composition of iron, nickel or chromium in the range, by weight, of 18 to 42% chromium, 18 to 48% nickel, the balance iron and other alloying additives, and typically is a high chromium stainless steel having about 31 to 38% chromium or a low chromium stainless steel having about 20 to 25% chromium.
- the substrates to which the MCrAlX overlay coating is applied typically are high chromium or low chromium stainless steel centrifugally cast or wrought tubes or fittings such as used in an ethylene furnace and the coating is applied to the inside surface of such products. It has been found that application of to coating by plasma transferred arc process deposition permits application of a continuous, uniformly thick and dense overlay coating throughout the length of the inside surfaces of the tubes and the fittings.
- a preferred MCrAlX is NiCrAlY which comprises, by weight, about 12 to 25% chromium, about 4 to 15% aluminium, about 0.5 to 1.5% yttrium, and the balance substantially nickel.
- the deposition process for the NiCrAlY coating involves the application of a powder raw material with a typical composition range of Cr 10 to 40 wt %, Al 3 to 30 wt %, Y up to 5 wt% with different mixtures of Ni, Co, Fe comprising the balance, by a plasma transferred arc process with the base alloy forming put of the electric circuit.
- a plasma arc melts both the powder and the alloy; argon being used as a carrier and shrouding gas to prevent oxidation.
- the process parameters are controlled during deposition to yield a melt puddle that will yield a coating with a desired thickness. By melting put of the substrate alloy, some dilution occurs which affects the final composition of the coating.
- the coating thus produced is dense, forms an alumina scale when exposed to air at high temperatures, and is tightly adhered to tube.
- the plasma transferred arc process can eliminate a separate aluminizing step.
- the material transfer method is highly efficient and between 80 to 90% of the raw material is incorporated into the coating, compared to between 25 and 30% with the method as described in patent pending 09/599,196.
- Two high temperature alloy stainless steel materials were used as substrates; one a H46M alloy the other one 900 B alloy.
- the coating was obtained from a NiCrAlY powder with a nominal composition in weight percentage of Al 10, Cr 22, Yl, Ni balance, with impurities comprising less than 1 wt %.
- the size distribution of the powder was as +45 microns ⁇ 106 microns. It was fed to the gun at a rate of 30 grams per minute using 100 amps and 50 volts across the arc.
- the coating was dense to continuous, over 4 mm thick, with a smooth interface as shown in FIG. 1 . No defects spanning from the base alloy to the coating surface were observed but some bubbles could be detected near the outer surface of the coaling.
- the composition reflected the fact that part of the alloy was melted, so the NiCrAlY got mixed and diluted with the elements present in the HTA. In both cases the aluminum content was between 5 to 7 wt %.
- the sample deposited on H46M had however less iron, more nickel and chromium than the sample deposited on 900B. Some other elements present in the base alloy such as silicon, niobium and manganese diffused into the coating but none amounted to more than 1 wt % on the welded layer. No heat treatment was given to these samples prior to their examination.
- the samples were aged in air at 1150° C. for up to 500 hours. After each aging period the samples were taken out of the oven and dipped in water to assess the thermal shock resistance of the ensemble. None of the samples spalled or cracked after such treatments.
- the bulk microstructure did not drastically change after any aging time, as indicated in FIGS. 2 and 3. However, at the free surfaces and at the interface new structures developed. A 10 microns thick alumina layer was formed on the outer surface which proved to drastically reduce the formation of catalytic coke in coated HTA alloys. In voids and other inner defects, a core of mixed oxides (Cr—Al—Ni—Y 0 ) was precipitated inside an alumina skin. The attack by oxygen extended several microns inside the coating.
- nitrides basically A1N, developed; these crystals grew in a dispersed manner as shown in FIGS. 4 and 5.
- the number of nitrides was larger in the sample prepared on the high chromium M46M alloy, probably due to a larger amount of nitrogen dissolved in the alloy. Even in this case, the nitrides did not agglomerate in a straight or continuous manner, hence reducing the possibility of a mechanical failure. This avoids the need for deposition of an interlayer whose main purpose was to absorb the nitrogen coming from the tube.
- the amount of aluminum in the bulk was reduced to just above five weight percent after 500 hours at aging at 1150° C., part of the original aluminum having diffused into the base alloy.
- NiCrAlY powders are applied by plasma transferred arc to high temperature alloys and the resulting interface layer is dense, continuous and smooth and forms an adherent metallurgical bond with the HTA substrate.
- Any precipitated nitrides and carbides are dispersed in and in proximity to the interface layer, obviating the need for heat treatment of the coating or the provision of a separate interlayer.
- Enough aluminum is available in the coating to form an alumina surface scale. After 500 hours of aging in air at 1150° C. and thermal shock tests, the composition and bulk structure changed only slightly. Nitrides formed near the interface layer, however, these are dispersed and will not result in coating delamination.
- the surface region showed evidence of oxidation, however, the attack was shallow and sufficient aluminum remained to maintain the protective alumina scale.
- the surface alloy of the invention on HTAs has particular utility in the coating of reactor tubes for use in high temperature corrosive environments such as furnaces for the production of ethylene.
Abstract
Description
Claims (21)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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US09/690,447 US6475647B1 (en) | 2000-10-18 | 2000-10-18 | Protective coating system for high temperature stainless steel |
AU2001267204A AU2001267204A1 (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
CA002357407A CA2357407C (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steels |
PCT/CA2001/000848 WO2001094664A2 (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
JP2002502200A JP4805523B2 (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
EP01944809A EP1292721A2 (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
KR1020027016497A KR20030024685A (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
CA2612881A CA2612881C (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
CA002614962A CA2614962A1 (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steels |
CN01810768A CN1433486A (en) | 2000-06-08 | 2001-06-08 | Coating system for high temperature stainless steel |
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